UV or EB Curing Screen Printing Inks Containing a High Amount of Renewable/Sustainable Material
The present invention relates to ink formulations, based on epoxidized vegetable oil or animal oil, which can be cured with UV-lamps or electron beams (EB) and which are suitable for industrial and commercial use.
Screen printing is widely used for printing on various kinds of substrates such as various kinds of papers, paper board, card board, textiles, leather, wood, glass, metal, and various plastic materials. Screen printing inks are characterized by a very high viscosity (compared for instance to gravure printing inks), i.e. they are usually paste-like.
With respect to the drying process of screen printing inks there are (1) physically drying inks which dry by evaporating solvents and other volatile components for instance in a continuous- flow dryer, and (2) chemically drying inks which dry by reactive or oxidative curing mechanisms. The chemically drying inks are usually inks where UV radiation or electron beams (EB) are used for initiating the curing.
UV or EB curing screen inks are typically made from materials, based on crude-oil chemistry. The binder systems of free radical curing systems are typically based on reactive acrylics, while the binder system of cationic curing systems are typicalh based on cycloaliphatic epoxides.
In our days it is, however, preferred to use renewable/sustainable materials also in printing inks.
It is known that epoxidized vegetable oils are suitable for cationic cure mechanism and are currently offered for wood coating applications. These systems, however, are not suitable for use as UV or EB curing inks in screen printing, because their reactivity is too low for typical curing conditions in screen printing apparatus. The screen printing industry typically uses doses from about 70 to 300 mJ/cm2, which usually is too low to effectively cure a pigmented system based on epoxidized vegetable oil.
It was therefore the object of the present invention to provide a printing ink for screen printing which contains a high amount of sustainable material but is curable with the usual energy doses of common screen printing apparatus.
This object is achieved by a printing ink composition comprising
(a) at least one epoxidized vegetable or epoxidized animal oil which is optionally further modified, and
(b) at least one reactive diluent selected from optionally substituted oxetanes and limonene diepoxide, wherein the amount of component (a) is 40 to 95 wt.-% based on the total ink composition, and the ink is characterized as suitable for screen printing.
The inks of the present invention are based on epoxidized vegetable or animal oils in combination with oxetanes or limonene diepoxide for screen ink applications and working conditions, that meet the requirements for their industrial use.
Trials have shown that this system works well under industrial conditions. Adhesion after 24 h is very good for commercial use and typically checked by tape & Crosshatch tests. There is a wide field of materials to print on with the inks of the present invention, such as, but not limited to: paper and board: plastics materials like PP, PE. PVC. PC: glass; metal; etc.
One of the essential features of the inks of the present invention is the high amount of sustainable material, an epoxidized vegetable oil or animal oil which is optionally further modified.
Epoxidized vegetable or animal oils and the production thereof are well -known for a long time and some are commercially available. With respect to epoxidized oils and their production reference is for instance made to US 2,569,502.
Suitable examples of epoxidized vegetable or animal oils are epoxidized soybean oil, epoxidized flax seed oil, epoxidized coconut oil, epoxidized chia oil, epoxidi/ed rapeseed oil, epoxidized palm oil, epoxidized perilla oil, epoxidized cottonseed oil, epoxidized linseed oil including epoxidized high Ω linseed oil, epoxidized lard oil. epoxidized peanut oil, epoxidized olive oil, epoxidized sunflower oil, epoxidized safflower oil, epoxidized castor oil, epoxidized neat's foot oil, epoxidized corn oil. epoxidized cocao oil, epoxidized hazelnut oil, epoxidized grape-seed oil, epoxidized almond oil. epoxidized wheat germ oik epoxidized menhaden oil,
epoxidized whale oil, epoxidized herring oil, and epoxidized lailemanlia oil. It is preferred that the oil contains a high content of unsaturated and polyunsaturated fatty acids as with such oils a high degree of epoxidation is possible.
According to one embodiment the oil to be used for epoxidation contains at least 20 wt.-% (poly)unsaturated fatty acids, more preferably at least 40 wt-%. even more preferred at least 50 wt.-% and most preferred at least 70 wt-%.
Preferred epoxidized oils of the foregoing are epoxidized linseed oil, epoxidized soybean oil, epoxidized safilower oil, epoxidized corn oil, and epoxidized lallemantia oil.
Also useful in the present invention are epoxidized vegetable or animal oils which are further modified. Suitable modifications are for instance prepolymerization. and copolymerization with other epoxy compounds, preferably prepolymerization.
The prepolymerization of oils and epoxidized oils is well-known and is for instance described in WO2004/063245.
Prepolymerized epoxidized oils can for instance be obtained by reacting the epoxidized oil with a poiycarboxylic acid or anhydride thereof and thereby obtaining a polyester pre-polymer. Examples of suitable poiycarboxylic acids are oxalic acid, maleic acid, succinic acid, chlorendic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hcxahydrophthalic anhydride, nadic anhydride, adipic acid, citraconics, terephthalic acid, isophthalic acid, sebacic acid, azelaic acid, mellitic acid, pyromellitic acid, fumaric acid, rtaconic acid, the alky] or alkenyl substituted succinic acids, the dimerized fatty acids, diglycolic acid, and various tricarboxylic acids such as 1,2.3-propane tricarboxylic acid, citric acid, trimellitic acid and trimesic acid, especially preferred are oxalic acid and maleic acid.
Other prepolymerization methods are reaction of the oil with (meth)acrylic acid, aliphatic \ inyl esters (like vinyl acetate) and alcohols.
As regards the epoxidation, the epoxidation degree is not particularly limited, and the oil can be fully epoxidized or only partially. The maximum degree of epoxidation is dependent on the content of (poly)unsaturated fatty acids in the oil. Preferably, the degree of epoxidation is 1 to 35% epoxide oxygen of the epoxidized oil, more preferably 5 to 25%, most preferably 8 to 20%. According to one embodiment the epoxide oxygen content is at least 9% based on the epoxidized oil.
The ink formulations of the present invention can contain one or more epoxidized optionally further modified vegetable or animal oils. If two or more are used they can differ in at least one of the following features: the kind of oil. the degree of epoxidation, the kind of modification, the degree of modification.
The amount of the epoxidized vegetable or animal oil(s) in the printing ink composition is 40 to 95 wt. -% based on the total ink composition, preferably 45 to 90 wt.-%, more preferably 50 to 80 wt.-%. If more than one epoxidized oil is used these ranges refer to the total amount of epoxidized optionally further modified vegetable/animal oils.
The other essential component of the inks according to the present invention is the reactive diluent which is selected from limonene diepoxide and oxetanes.
Oxetanes are cyclic ethers that very efficiently polymerize with high reaction speeds. Oxetanes have a high diluting power and can have a strong positive effect on other properties, such as adhesion, chemical resistance, gas barrier and others Oxetanes useful in the present invention include monofunctlonal and multifunctional oxetanes. i.e. compounds with one or more oxetane groups. Examples are 3-ethyl-3-hydroxymethyloxelane (also known as trimethylolpropyl oxetane or TMPO), bisj(3-mcthyIo\etan-3-yl)methyi]ether. bJs[(l -efhyl-3- oxetany])melh\ i] ether (also abbreviated as DOX). 3-ethyl-3-[(2-ethylhe\ylox>)methyl]oxetane.
lmethox\)mcthyl]ben7Cne. trans-3-tert-butyl-2-phen>loxetane.
3.3A4-tetrameth\l-2.2-diphenyIoxetane. di[3-ethyl(2-methoxy-3-o\etanyl)jmeth>lether. 1.4- bis(2,3.4.4-tetrameth\l-3-ethyloxetan\l)butane, 1.4-bis(3-methyl-3-ethyio\etanyl)butane. di(3.4.4-trimethyi-3-cthyIoxetan\])butane, 3-(2-cthylhex\ lox\methvi)-2.2.3.4- tetramelh) loxctane. 2-(2-ethylhcx\lox\)-2,3,3.4.4-pentamelh>]oxetane. 4.4
*-bis[(2.4-dimcthyl- 3-ethyl-3-oxetanyl)methox>]biphenyl. 1.7-bis{2.3.3,4,4-pentameth} loxetanyl-heptane)oxetan\L 2-methoxy-3.3-dimethyloxetane. 2,2.3.3-tetramethyloxetane.
di methyl oxetane, di(2-(4-melhoxyphenyI)-3-methyloxetane-3-yl)ether.
In principle, the suitable oxetanes can be classified as oxetane compounds with one oxetane ring optionally having (a) substitucnt(s), and oxetane compounds with 2 or more oxetane rings each optionally having (a) substituent(s); the substituent(s) can for instance be present in 2-position or 3-position. Suitable substituents of the mono- and multifunctional oxetanes are for instance Ci-Cg alkyl and C1-Cg alkoxy.
The most preferred oxetanes are TMPO and DOX. From an economical point of view TMPO is even more preferred.
Suitable oxetanes and references with respect to their preparation are for instance found in US2005/0119361 Al . Some oxetanes are also commercially available from Perstorp/SE and DKSH/Hamburg.
Limonene diepoxide (also known as dipentene dioxide) is another suitable reactive diluent. By the use thereof the content of sustainable materials in the printing ink is further increased.
The ink compositions of the present invention can contain one or more reactive diluents. If two or more reactive diluents are used they can be mixtures of different oxetanes or mixtures of oxetane(s) and limonene diepoxide.
The amount of the reactive dϊluent(s) is not particularly limited. Preferably it is 5 to 25 wt.-% based on the total ink composition, more preferably 10 to 20 wt-% and most preferably 8 to 15 wt.-%. If two or more reactive diluents are used these ranges refer to the total amount of them.
The inks according to the present invention optionally include a colorant which can be selected from all grades and types of organic and inorganic pigments and dyes which are suitable for use in screen printing ink applications.
Examples of the colorant include carbon blacks such as acetylene black, channel black and furnace black; metal powders such as an aluminum powder and bronze powder: inorganic pigments such as red oxides, yellow lead, ultramarine blue, chromium oxides and titanium oxides: and organic pigments such as a/o pigments (including insoluble azo pigments, azolake pigments and condensed azo pigments), phthalocyanine pigments like metal-free phthalocyanine pigment and copper phthaiocyanine pigment), anthraquinone dyes, quinacridon dyes, isoindolinone d>es, isoindoline dyes, dioxadin dyes, threne dyes, perylene dyes, perynonc dyes, thioindigo dyes, quinophthalone dyes and metallic complexes; lakes of acid or basic dyes; oil-soluble dyes such as diazo dyes and anthraquinone dyes; and fluorescent pigments. Suitable pigments can be crude pigments as well as conditioned pigments.
The colorant exists in the ink usually in a dispersed state. The average particle diameter of the dispersed colorant in the ink is not particularly limited and can be a suitable size according to the purpose, while it is preferably in the range of 1 μm to 20 μm and more preferably 5 μm to 10 μm.
The added amount of the colorant is not particularly limited, and can be set at a suitable level in accordance with the purpose, while it is preferably in the range of 0.5 wt.-% to 15 wt.-% based on the total weight of the ink. more preferably 2 wt.-% to 10 wt.-%.
According to one embodiment the ink compositions according to the invention are intended for curing by EB. In such a case no cationic photo initiator is necessary in the ink composition. According to another embodiment the ink compositions according to the invention are photocurable, and most preferably are UV-curable, and accordingly contain a suitable cationic photoinitiator (i.e. a photoinitiator which is capable of initiating a cationic cure mechanism).
For photocuring compositions such as UV-curing compositions, a wide range of commercially available cationic photo initiators can be incorporated to initiate the cationic photocure mechanism. The amount of the cationic photoinitiator(s) is not particularly limited but is typically from 0.5 to 20 wt.-%, for example from 1 to 14 wt.-%, by weight of the total ink composition.
Suitable cationic photoinitiator s include
salts that can have a photochemically-reactive cationic portion and a non-nucleophilic anion. A broad class of cationic photoinitiators can be used, including those described in I
1S 4.250.31 1. US 3.708,296. US 4.069.055. US 4.216.288. US 5.084.586. US 5.124.417. US 4.985.340. and US 5.089.536. the descriptions of which are incorporated herein by reference.
Suitable cations include organic onium cations, organometallic complex cations, and the like. Useful organic onium cations include, for example, sulfoxonium. iodonium like diaryliodonium. sulfonium like triarylsulfonium. carbonium. and phosphom
'um. Most preferred are 1- and S-centered onium salts (for example, diaryliodonium and triarylsulfonium). The
group of such salts can be an unsubstituted or substituted aromatic moiety having up to about four independently selected substituents. The substituents preferably have fewer than about 30 carbon atoms and up to about 10 heteroatoms selected from N, S. non-peroxidic O, P, As, Si, Sn, B, Ge, Te, Se, and the like. Examples of such substituents include hydrocarbyl groups (such as methyl, ethyl, butyl, dodecyl, tetracosanyl, benzyl, allyl, benzylidene, ethenyl. and ethynyl); hydrocarbyloxy groups (such as methoxy, butoxy and phenoxy); hydro car bylmercapto groups (such as methyimercapto and phenylmercapto); hydrocarbyloxy carbonyl groups (such as oxycarbonyl and phenoxycarbonyl); hydrocarbylcarbonyloxy groups (such as acetoxy and cyclohexanecarbonyloxy); hydrocarbylcarbon amide groups {such as acetamido and benzamido); azo; boryl; halo groups (such as chloro, bromo, iodo and fluoro); hydroxy; oxy; diphenylarsino; diphenylstibino; trimethylgermano; trimethylsiloxy; and aromatic groups (such
as cyclopentadienyl. phenyl, lolyl. naphthyl. and indenyl). In sulfonium salts, it is possible for a substituent to be further substituted with a thioether or thioether-conlaining sulfonium cation (for example, diphenyl [4- (phenyl thio)phenyl] sulfonium and (thiodiphenylene)bis- diphenylsul fonium) .
Useful organometallic complex cations include those described in US 4,985,340, the description of which are incorporated herein by reference, and represented by the formula:
[(L'XL^MΓ (I)
wherein M is a metal selected from the group consisting of Cr. Mo, W. Mn. Re. Fe, Ru. Os, Co, Rh
5 Ir, Pd. Pt, and Ni (preferably, selected from Cr. Mo
5 W, Mn, Fe. Ru. Co. Pd. and Ni: and, most preferably, from Mn and Fe); L
1 represents 1 or 2 cyclic, polyunsaturated ligands independently selected from the group consisting of substituted and unsubstituted cyclopentadienyl, cyclohexadienyl. cycloheptatrienyl, cyclooctatetraenyl, heterocyclic compounds, and aromatic compounds selected from substituted or unsubstituted arene compounds, and compounds having 2 to 4 fused rings, and units of polymer (for example, a phenyl group of polystyrene, poly(styrene-co-butadiene), poly(styrene-co-methyl methacrylatc).
and the like: a cyclopentadiene group of ρoiy(vinylcyclopentadienc): a pyridine group of poly(v
and the like, each capable of contributing 3 to 8 electrons to the \alence shell of M; L
" represents none, or 1 to 3 nonanionic ligands contributing an even number of electrons and independently selected from the group consisting of carbon monoxide, ketones, olefins, ethers, nitrosonium. phosphines, phosphites, and related derivatives of arsenic and antimony, organonitriles. amines, alkynes. isonitrilcs. dinitrogen. and the like, with the proviso that the total electronic charge contributed to M results in a net residual positive charge of q to the complex cation; and q is an integer of 1 or 2.
Useful anionic portions of the photoinitiators include those that can be represented by Xn, where X Is an anion selected from the group consisting of tris-R< sulfonyl methide. bis-Rf sulfonyl imide, tris-(fluorinated aryl)sulfonyl methide, tetrakis-(fluorinated aryl) borate and organic sulfonate anions, wherein each Rf is independently selected from the group consisting of fluorinated or perfiuorinaled (preferably, perfluorinated) alkyl radicals having from 1 to about 20 carbon atoms, fluorinated aryl radicals having from 6 to about 10 carbon atoms, and ring structures formed from two said fluorinated or perfluorinated alkyl radicals joined together to form a unitary alkylene radical having 5 or 6 ring atoms, said radicals optionally containing one or more divalent oxygen, trivalent nitrogen, or divalent sulfur atoms; and n is an integer of 1 or 2 (the number of complex anions required to neutralize the charge "q" on the complex cation).
Examples of such anions are described in US 5,554.664, the description of which is incorporated herein by reference. Useful anions also include those described in US 6,265,459, the description of which is incorporated herein by reference,
In addition to those described above, suitable anions, X, for use as the counterion to the above- described cations include those represented by the formula
DQr (II)
wherein D is a metal from Groups IB to VIIB and VIII or a metal or metalloid from Groups IllA to VA of the Periodic Table of Elements (CAS notation): Q is a halogen atom, a hydroxyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted alkyl group; and r is an integer of 1 to 6. Preferably. D is selected from metals such as copper, zinc, titanium, vanadium, chromium, aluminum, tin. gallium, zirconium, indium, manganese, iron, cobalt, and nickel, or from metalloids such as boron, antimony, arsenic, and phosphorus. Preferably. Q is a halogen atom (more preferably, chlorine or fluorine). Representative examples of such anions include B(phenyl)f, B (phenyl)
. ^ (alky 1)
~( where alkyl can be ethyl, propyl, butyl, hexyl. and the like). BF
4 ". PF
6 ". AsF
6 ". SbF
6 ". FeCl
4 ", SnCl
5 ". SbF.OH
". AlCLf, AlF
6 "- GaCl
4 ". InF
4 ", TiF
6 ". ZrF
6 ". B(C
6F
^)
4 ", and B(C
6r
3(CF
?)
2)f . Preferred anions include BF
4 . PF
6 ", AsF
6 ". SbF
6 ". SbF
5OFI
". B(C
6F
5V. B(C
6F
3(CF
3)
2)f. and
Other anions, X. useful in suitable photoinitiators include CFhSOf. CF3SOs". C6H^SO3 . p- toluenesiilfonate. p-chlorobenzenesulfonate. and the like. Preferred anions include BF4 ". PFf,". SbF6 ", SbF.OIT". AsF6 ". SbCl6 ", CF3SOf . C(SO2CF3)f . and N(SO2CFO:".
Preferred cationic photoinitiators are triarylsulfonium salts like triarylsuUbnium hexafluorophosphates and iodonium salts like iodonium hexafluorophosphates.
Suitable cationic photoinitiators are commercially available or can be prepared by known methods.
The compositions of the present invention can optionally also contain one or more free radical photoinitiators which may be suitable as curing accelerators. If they are used their total amount is preferably 0.1 to 5 wt.-% based on the total ink composition, more preferably 0.5 to 2.5 wt.- %.
Suitable free radical photoinitiators include, for example 2,4,6-lrimethylbenzyl diphenyi phosphine oxide (Lucerin™ TPO, BASF), bis(2,4,6~trimethyibenzoyl)phenyl phosphine oxide
(Irgacure 819. Ciba Geigy), bis(2,6~dimethoxybenzoyl)-2,4,4-triτncthylpcntyl phosphine oxide, ethyl-234,f)-trimethy!ben/oylphenyl-phosphinate (Lucerin™ TPO-L, BASF), 2-benzyl-2- dimcthy]ammo- l -(4-morpho1inphenyl)butan-J -one (Irgacure™ 369, Ciba Geigy), 1 - liydroxycyclohexyl acetophenone (IrgacureI M 184, Ciba Geigy), iso-propyl thioxanthonc (Quantacure™ ITX, IBIS or Speedcure™ ITX, Lamb son); 2-chloro thioxanthone (Kayacure™ CTX, Nippon Kayaku), ohgo[2-hydroxy-2-methyl~l-[4-(l~methyivinyl)phenyl]propanone] and 2-hydroxy-2-mcthyl-l -phenyl- 1 -propanone (Esacurc™ KIPlOOF. Lamberti), methyl benzoyl formate (Gcnocurc MBF Rahn), benzophenone, 2-melhyl-l -[4-(methylthio)phenyl]-2- moipholinopropan-1-onc (Irgacure tM 907, Ciba Geigy), 2-isopropylthioxanthone. anthracene and derivatives thereof.
A person skilled in the art can find the optimum cure accelerator for a certain ink formulation by suitable experiments. According to one embodiment iodoniυm salts may be used as cation) c photoinitiator in combination with a hydroxyketon as curing accelerator (radical photoinitiator).
Further Optional Additives:
If desired, adhesion promotes like inert or passive resins such as acrylics, styrerte acrylatcs, polyesters, polycarbonates or celluloses may be included in the ink in small amounts in order to improve the adhesion of the ink coating. If included, for example an amount not exceeding 15%. and preferably not exceeding 10%, by weight of the composition is used.
The inks of the present invention can optionally contain one or more (meth)acrylic monomers usually used in screen printing inks. In view of the object of using a high amount of sustainable material it is, however, preferred that the amount of (meth)acrylic monomers is less than 5 wt.~% based on the total ink composition and it is preferred that no acrylic monomers are present.
Additives such as wetting agents, silicone and non-silicone antifoams may be incorporated to improved print properties such as substrate wetting and flow-out, and may be included in an amount of preferably from 0 to 5%, more preferably from 0 to 2%, by weight of the ink composition.
Fillers may be included to control the viscosity and rheology of the ink composition typically to improve printing characteristics, and may be present preferably in an amount of from 0 to 40%, more preferably from 0 to 30%, by weight of the ink composition, most preferably 0 to 10 wt.-%.
Suitable fillers include, but are not limited to, china clay, talc, barium sulphate, aluminium silicate, and silica.
It will be appreciated that the compositions according to the invention will be substantially free of organic solvents like petroleum -based solvents. However, small amounts of organic solvent may be included, if needed, in amounts not exceeding 10%, and preferably not exceeding 5%, by weight of the composition. Most preferred is that the composition is free of organic solvent. According to another embodiment, the composition is substantially free of water (i.e. contains not more than 5 wt.-% water, preferably not more than 1 wt.-%).
Further suitable optional additives arc anti-skinning agents; levelling agents; cure accelerators; flrc-rctardants; rheological modifiers; etc.
Jf the ink composition is intended for single colour screen printing epoxidized vegetable or animal oils and modified epoxidized vegetable and animal oils are suitable.
For multi-colour screen printing epoxidized oils and further modified epoxidized oils can be used, however, it is preferred to use prepoiymerized epoxidized oils as they need less energy for sufficiently curing the ink before the next ink is applied.
Usual energy values are between 30 and 600 niJ/cm2, preferably 50 to 400 mJ/cm2 and more preferably 80 to 200 mj/cra2. Conventional UV curing units containing FIg lamps can be used for curing the inks of ihe present invention.
The ink compositions of the present invention are intended for use in screen printing. Accordingly, their viscosity is relatively high (often pasiy) compared to inks for other printing methods such as gravur printing or ink jet printing. Preferably, the viscosity of inks according to the present invention is 1 to 20 Pa-s at a shear rate of 3 s~! when measured with a rotational viscometer of the plate-cone type (cone geometry: 2°/40mm) at 200C (as is for instance available from Bohlin Instruments); when measured at a shear rate of 150 s"' at 200C with the plate-cone rotational viscometer (cone geometry: 2°/40mm) the viscosity is preferably 0.5 to 15 Pa-s. More preferably the viscosity is 4 to 15 Pa-s at 3 s" 1; at 150 sA the viscosity is more preferably and 1 to 12 Pa-s.
Characteristic for screen printing inks in general and therefore also for the inks of the present invention is that the viscosity decreases with increasing shear rate.
The viscosity of the inks according to the present invention can be adjusted to the specific screen printing method. Usually the viscosity of a line colour is from 3 to 10 Pa-s at 3 s"' and 1
Io 8 Pa-s ai 150 s"1 when measured as described above, while the viscosity of a process colour is usually from 8 to 15 Pa-s at 3 s"! and 5 to 10 Pa-s at 150 s"1 when measured as described above.
Epoxidized oils suitable for the present invention depending on the kind of oil and the degree of epoxidation may have a viscosity of about 0.8 to 2 Pa-s when measured at 2O0C with a shear rate of 6.42 s" 1 with a viscometer as described above; by prepolymerizing the epoxidized oils their viscosity increases depending on the degree of prcpolymerization to about 4 to 15 Pa-s at 20°C and a shear rate of 6.42 s" 1.
It is the intention of the present inventors that each feature (like compounds, amounts etc.) and embodiment described above can be combined with any other feature or embodiment described although not each and every combination is explicitly mentioned above.
EXAMPLES
The following inks were prepared according to conventional methods for preparing screen inks.
Example 1 : Blue Screen printing ink
Epoxidized vegetable oil1 71 .50
CM. pigment blue 15:3. pigment paste (25%) 6 00
TV1PO: 15.00
U vac U re UVI-69923 5.00
Silica 1.50
Defoamer/Levelling Agent 1.00
Total 100.00 wt- %
Example 2: Blue Screen printing ink
Epoxidjzed vegetable oil1 77.50 CL pigment blue 15:3, pigment paste (25%) 2.00
TMPO2 12.00
Uvacure UV1-69923 4.00
Silica4 3.00
Defoamer/Levelling Agent5 1 .00
ITX6 0.50
Total 100.00 wt-%
Example 3: Blue Screen printing ink with Filler/Extender
Epoxidized vegetable oil1 51.70
C.I. pigment blue 15:3, pigment paste (25%) 1.00
TMPO2 8.50
Uvacure UVf-69923 3.00
Silica4 0.70
Dcfoamcr/ Level] ing Agent ^ 0 70
ITX6 0.40
Silicate 34.00
Total 100.00 wt.-%
Dracowol EP 10/1 available from Dracosa AG, Wolfen (epoxidized lallemantia oil) 2 tπmethylolpropyl oxctane. available from Perstorp cationic photoinitiator, available from Union Carbide 4 filler, HDK-N20, available from Wacker AG ' Coalosil 100 E, available from Wittco 6 free radical LJV photoinitiator (2-isopropyl-thioxanthone)
Example 4: Blue Screen printing ink
Example I was repeated, however, Dracowol EP 10/1 was replaced by epovidized lallemantia oil which had been prepolymcrized by using oxalic acid (viscosity: 0.6 Pa-s when measured at 200C with a shear rate of 6.42 s"1 with a rotational viscometer as described above; compared to 1.1 Pa-s for Dracowol EP 10/1).
Example 5: Blue Screen printing ink
Example 1 was repeated, however, Dracowol EP 30/1 was replaced by epoxidized linseed oil.
Example 6: Blue Screen printing ink
Example 1 was repealed, however, TMPO was replaced by DOX.
Example 7: Blue Screen printing ink
Example 1 was repeated, however, TMPO was replaced by limonene diepoxide.
Example 8: Printing tests
The screen printing inks of the examples above were tested with a printing press (Thicmc Model 5020) useful for 5-colour-printing. As substrates soft PVC adhesive films, hard PVC plates, polypropylene plates, paper and board were used.
For drying/curing 2 UV lamps were used. The first lamp was adjusted to 80 W/cm, while the second one was adjusted to about 50 W/cm. The scan dryer speed was 50 m/min resulting in an energy dose of about 150 mi /cm2.
The obtained printing speeds arc within the presently acceptable ranges although the inks avoided acrylates and instead thereof contained a high content of sustainable materials. The inks of the present invention are, therefore, suitable for commercial/industrial sorecn printing.